The Quadrilátero Ferrífero, Brazil, is presently the largest accumulation of single itabirite-hosted iron ore bodies worldwide. Detailed petrography of selected hypogene high-grade iron ore bodies at, e.g. the Águas Claras, Conceição, Pau Branco and Pico deposits revealed different iron oxide generations, from oldest to youngest: magnetite → martite (hematite pseudomorph after magnetite) → granoblastic (recrystallised) → microplaty (fine-grained, 100 μm) hematite. Laser-fluorination oxygen isotope analyses of selected iron ore species showed that the δ18O composition of ore-hosted martite ranges between -4.4 and 0.9 ‰ and is up to 11 ‰ depleted in 18O relative to hematite of the host itabirite. During the modification of iron ore and the formation of new iron oxide generations (e.g. microplaty and specular hematite), an increase of up to 8 ‰ in δ18O values is recorded. Calculated δ18O values of hydrothermal fluids in equilibrium with the iron oxide species indicate: (1) the involvement of isotopically light fluids (e.g. meteoric water or brines) during the upgrade from itabirite-hosted hematite to high-grade iron ore-hosted martite and (2) a minor positive shift in δ18Ofluid values from martite to specular hematite as result of modified meteoric water or brines with slightly elevated δ18O values and/or the infiltration of small volumes of isotopically heavy (metamorphic and/or magmatic) fluids into the iron ore system. The circulation of large fluid volumes that cause the systematic decrease of 18O/16O ratios from itabirite to high-grade iron ore requires the presence of, e.g. extensive faults and/or large-scale folds. © 2013 Springer-Verlag Berlin Heidelberg.